Catalysis of cross-linking

Abstract

Disclosed is use of catalysts for chain extension and/or cross-linking of oligomers or polymers comprising carbon-carbon triple bonds.

The invention claimed is: 
     
       1. A method of chain extending and/or cross-linking an oligomer or a polymer comprising a carbon-carbon triple bond, the method comprising the step of:
 heating the oligomer or polymer in the presence of a cyclic aliphatic tertiary amine, a heteroaryl comprising at least one nitrogen atom within the aromatic ring, which nitrogen atom has one electron pair being part of the delocalized aromatic electrons and one electron pair not being part of the delocalized aromatic electrons, or a tertiary nucleophilic organophosphorus compound, wherein said carbon-carbon triple bond is conjugated with a group selected from the group consisting of —C(O)—, —C(O)O—, —C(O)NH—, —C(O)NC1-5 alkyl, 
 
       
         
           
           
               
               
           
         
       
       —SO 2 —, and -Ph. 
     
     
       2. The method according to  claim 1 , wherein said oligomer or a polymer comprises a phenylethenyl group, a propynoyl group, and/or a group comprising a phenylethenyl group and a propynoyl group. 
     
     
       3. The use method according to  claim 1 , wherein said cyclic aliphatic tertiary amine or said heteroaryl do not comprise any nitrogen atoms having substitutable hydrogen atoms, and wherein said heteroaryl only comprises carbon, nitrogen, optionally oxygen, and covalently bonded hydrogen atoms and wherein said heteroaryl is unsubstituted or wherein it is substituted with one or more groups, independently selected from the group consisting of —OC1-5 alkyl, —N(C1-5 alkyl) 2 , and C1-5 alkyl. 
     
     
       4. The method according to  claim 1 , wherein said catalyst is said heteroaryl and said heteroaryl is mono-cyclic. 
     
     
       5. The method according to  claim 4 , wherein said heteroaryl is a compound according to any one of the formulas (Xa) to (Xj), 
       
         
           
           
               
               
           
         
         wherein 
         A1 is NC1-5 alkyl, or “O” (oxygen); 
         A2 to A6 is independently selected from CH, CR10, and “N” (nitrogen), wherein at least two of A2 to A6 are, independent of each other, CH or CR10; 
         “n” is an integer of 0 (zero) to 3; and 
         R10 is selected, independently if more than one R10 is present, from C1-5 alkyl, OC1-5 alkyl, N(C1-5 alkyl) 2 , and phenyl. 
       
     
     
       6. The method according to  claim 5 , wherein A1 is NC1-5 alkyl, and the integer “n” is 0 (zero) or 1. 
     
     
       7. The method according to  claim 4 , wherein said heteroaryl is 4-dimethylaminopyridine, or 1-methylimidazole. 
     
     
       8. The method according to  claim 1 , wherein said catalyst is said tertiary nucleophilic organophosphorus compound and said tertiary nucleophilic organophosphorus compound is a compound according to formula (XII)
   PR 15 R 16 R 17   (XII)
 
 wherein R15, R16, and R17 are, independently of each other, selected from the group consisting of C1-5 alkyl, phenyl, OC1-5 alkyl, and Ophenyl. 
 
     
     
       9. The method according to  claim 8 , wherein said tertiary nucleophilic organophosphorus compound is selected from the group consisting of triphenylphosphine (PPh 3 ), tributylphosphine (PBu 3 ), trimethylphosphine (PMe 3 ), phenyl dimethylphosphine (PPhMe 2 ), and triphenylphosphite (P(OPh) 3 ). 
     
     
       10. The method according to  claim 1 , wherein said catalyst is 1,4-diazabicyclo[2.2.2]octane. 
     
     
       11. The method according to  claim 1 , wherein said oligomer or polymer is heated in the presence of a further compound according to formula (I) or (II), 
       
         
           
           
               
               
           
         
         wherein 
         R1 and R2, independently of each other, are hydrogen or C1-4 alkyl; 
         R4 and R5, independently of each other, are C1-5 alkyl or OC1-5 alkyl; 
         A is O, NC1-5 alkyl, or CH2; and 
         R6 is C1-5 alkyl or OC1-5 alkyl; 
         as a co-catalyst. 
       
     
     
       12. The method according to  claim 1 , wherein said heating is performed in the presence of at least 5 mole percent of said catalyst with respect to the amount of triple bonds to be chain extended and/or cross-linked. 
     
     
       13. The method according to  claim 1 , wherein said oligomer or said polymer is an oligo- or polyimide, a polyamide or an epoxy resin. 
     
     
       14. The method according to  claim 1 , wherein said oligomer or said polymer is obtainable by use of PEPA (phenylethynyl phtalic anhydride), EPA (ethynyl phtalic anhydride), 5,5′-(ethyne-1,2-diyl)bis(isobenzofuran-1,3-dione), 5-(prop-1-yn-1-yl)isobenzofuran-1,3-dione and/or 5-(3-phenylprop-2-ynoyl)isobenzofuran-1,3-dione. 
     
     
       15. The method according to  claim 1 , wherein said oligomer or said polymer is:
 an oligomer or a polymer comprising a residue according to formula (IVa) and/or (IVb), 
 
       
         
           
           
               
               
           
         
         wherein 
         R25 is hydrogen, C1-5 alkyl, or phenyl, wherein said phenyl optionally is substituted by halogen, C1-5-alkyl, and/or trifluoromethyl; and 
         the waved line(s) indicate(s) the point of attachment(s) to said oligomer or said polymer; 
         an oligomer or a polymer comprising a residue according to formula (IVa1), (IVa2), (IVa3), (IVb1), (IVb2) or (IVb3), 
       
       
         
           
           
               
               
           
         
         wherein 
         R25 is hydrogen, C1-5 alkyl, such as methyl, or phenyl, which phenyl optionally is substituted by halogen, C1-5-alkyl, trifluoromethyl; and 
         the waved line(s) indicate(s) the point of attachment(s) to the oligomer or the polymer; 
         a residue according to formula (IV), 
       
       
         
           
           
               
               
           
         
         wherein 
         the waved line indicates the point of attachment to the oligomer or the polymer; 
         “Ar” is an aryl or a heteroaryl; 
         R3 is, independently if “n” is 2 or more, selected from the group consisting of C1-4 alkyl, OC1-4 alkyl, halogen, cyano, nitro, C1-4 fluoroalkyl; 
         the substituent(s) R3 may be connected to any substitutable atom(s) of “Ar”; and 
         “n” is an integer from 0 (zero) to 5; or 
         an oligomer or a polymer comprising a residue according to formula (IV1), (IV2) or (IV3), 
       
       
         
           
           
               
               
           
         
         wherein 
         the waved line indicates the point of attachment to the oligomer or the polymer; 
         “Ar” is an aryl, such a phenyl, or a heteroaryl; 
         R3 is, independently if “n” is 2 or more, selected from the group consisting of C1-4 alkyl, OC1-4 alkyl, halogen, cyano, nitro, C1-4 fluoroalkyl; 
         the substituent(s) R3 may be connected to any substitutable atom(s) of “Ar”; and 
         “n” is an integer from 0 (zero) to 5. 
       
     
     
       16. The method according to  claim 13 , wherein said oligomer or said polymer is an oligo- or polyimide comprising at least one residue of an aromatic dianhydride and at least one residue of an aromatic diamine,
 wherein said aromatic diamine is 1,4-diaminobenzene, 1,3-diaminobenzene, or a diamine according to the general formula (XXI) 
 
       
         
           
           
               
               
           
         
         wherein 
         the amino groups are connected to any substitutable carbon atom in the benzene residues; and 
         “L” is a direct bond or a moiety selected from the group consisting of —O—, —S—, —C(O)—, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —CH 2 —, 3-oxyphenoxy, 4-oxyphenoxy group, 4′-oxy-4-biphenoxy group, and 4-[1-(4-oxyphenyl)-1-methylethyl]phenoxy group; and 
         wherein said aromatic dianhydride is pyromellitic dianhydride or a dianhydride according to the general formula (XX), 
       
       
         
           
           
               
               
           
         
         wherein 
         “G” represents a direct bond or a di-valent group selected from the group consisting of a carbonyl group, a methylene group, a sulfone group, a sulfide group, an ether group, an —C(O)-phenylene-C(O)— group, an isopropylidene group, a hexafluoroisopropylidene group, a 3-oxyphenoxy group, a 4-oxyphenoxy group, a 4′-oxy-4-biphenoxy group, and a 4-[1-(4-oxyphenyl)-1-methylethyl]phenoxy group; and 
         “G” is connected to the 4- or 5-position and the 4″- or the 5″-position, respectively, in the isobenzofuran-1,3-dione residues. 
       
     
     
       17. The method according to  claim 16 , wherein
 said aromatic diamine is selected from the group consisting of pyromellitic dianhydride, 4,4′-oxydiphthalic anhydride, 2,2-bis-[4-(3,4-dicarboxyphenoxy)phenyl]-propane dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic acid dianhydride, 3,3′,4,4′-tetracarboxybiphenyl dianhydride, 4,4′,5,5′-sulfonyldiphthalic anhydride, and 5,5′-(perfluoropropane-2,2-diyl)bis(isobenzofuran-1,3-dione); and 
 said aromatic diamine selected from the group consisting of 4,4′-oxydianiline, 1,4-diaminobenzene, 1,3-diaminobenzene, 1,3-bis-(4-aminophenoxy)benzene, 1,3-bis-(3-aminophenoxy)benzene, methylenedianiline, and 3,4′-oxydianiline. 
 
     
     
       18. An intermediate composition for use in the process of  claim 1 , the composition comprising a cyclic aliphatic tertiary amine, a heteroaryl comprising at least one nitrogen atom within the aromatic ring, which nitrogen atom has one electron pair being part of the delocalized aromatic electrons and one electron pair not being part of the delocalized aromatic electrons, or a tertiary nucleophilic organophosphorus compound optionally a co-catalyst, an oligomer or a polymer comprising a carbon-carbon triple bond, wherein said carbon-carbon triple bond is conjugated with a group selected from the group consisting of —C(O)—, —C(O)O—, —C(O)NH—, —C(O)NC1-5 alkyl, 
       
         
           
           
               
               
           
         
       
       —SO 2 —, and -Ph and optionally a solvent. 
     
     
       19. The method according to  claim 1 , wherein said cyclic aliphatic tertiary amine, said nucleophilic heteroaryl or said tertiary nucleophilic organophosphorus compound, any co-catalyst and/or any solvent present, is, at least partly, evaporated during and/or subsequent to the chain extension and/or cross-linking.